Tridentate ligand

ABSTRACT

Certain 2,6-pyridinecarboxaldehydebis(imine) and 2,6-diacylpyridinebis(imine) compounds are provided, which are particularly suitable for use as tridentate ligands in iron and cobalt olefin polymerization catalysts.

CROSS-REFERENCE TO RELATED APPLICATIONS

1. This application is a continuation-in-part of co-pending applicationSer. No. 09/273,409, filed Mar. 22, 1999, which is acontinuation-in-part of application Ser. No. 08/991,372, filed Dec. 16,1997, now U.S. Pat. No. 5,955,555, which claims the benefit ofProvisional Application No. 60/033,656, filed Dec. 17, 1996.

FIELD OF THE INVENTION

2. Polymers with varied and useful properties may be produced inprocesses using at least two polymerization catalysts, at least one ofwhich is a selected iron or cobalt catalyst, for the synthesis ofpolyolefins.

TECHNICAL BACKGROUND

3. Polyolefins are most often prepared by polymerization processes inwhich a transition metal containing catalyst system is used. Dependingon the process conditions used and the catalyst system chosen, polymers,even those made from the same monomer(s) may have varying properties.Some of the properties which may change are molecular weight andmolecular weight distribution, crystallinity, melting point, branching,and glass transition temperature. Except for molecular weight andmolecular weight distribution, branching can affect all the otherproperties mentioned.

4. It is known that certain transition metal containing polymerizationcatalysts containing iron or cobalt, are especially useful inpolymerizing ethylene and propylene, see for instance U.S. Patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No.5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No.6,150,482) (“equivalents” of World Patent Applications 98/27124 and98/30612). It is also known that blends of distinct polymers, that varyfor instance in molecular weight, molecular weight distribution,crystallinity, and/or branching, may have advantageous propertiescompared to “single” polymers. For instance it is known that polymerswith broad or bimodal molecular weight distributions may often be meltprocessed (be shaped) more easily than narrower molecular weightdistribution polymers. Also, thermoplastics such as crystalline polymersmay often be toughened by blending with elastomeric polymers.

5. Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

6. Various reports of “simultaneous” oligomerization and polymerizationof ethylene to form (in most cases) branched polyethylenes have appearedin the literature, see for instance World Patent Application 90/15085,U.S. Pat. Nos. 5,753,785, 5,856,610, 5,686,542, 5,137,994, and5,071,927, C. Denger, et al,. Makromol. Chem. Rapid Commun., vol. 12, p.697-701 (1991), and E. A. Benham, et al., Polymer Engineering andScience, vol. 28, p. 1469-1472 (1988). None of these referencesspecifically describes any of the processes herein or any of thebranched homopolyethylenes claimed herein.

SUMMARY OF THE INVENTION

7. This invention concerns a process for the polymerization of olefins,comprising, contacting under polymerizing conditions:

8. (a) a first active polymerization catalyst for said olefins which isa Fe or Co complex of a ligand of the formula:

9. wherein:

10. R¹, R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or an inert functional group;

11. R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inertfunctional group or substituted hydrocarbyl; and

12. R⁶ and R⁷ are aryl or substituted aryl;

13. (b) a second active polymerization catalyst for said olefins whichcontains one or more transition metals;

14. (c) a least one first olefin capable of being polymerized by saidfirst active polymerization catalyst; and

15. (d) at least one second olefin capable of being polymerized by saidsecond active polymerization catalyst.

16. This invention also concerns a process for the polymerization ofolefins, comprising, contacting under polymerizing conditions:

17. (a) a first active polymerization catalyst for said olefins which isa Fe or Co complex of a ligand of the formula:

18. wherein:

19. R¹, R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or an inert functional group;

20. R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inertfunctional group or substituted hydrocarbyl; and

21. R⁶ and R⁷ are aryl or substituted aryl;

22. (b) a second active polymerization catalyst for said olefins whichcontains one or more transition metals;

23. (c) a least one first olefin capable of being polymerized by saidfirst active polymerization catalyst; and

24. (d) at least one second olefin capable of being polymerized by saidsecond active polymerization catalyst;

25. and provided that:

26. one or both of said first olefin and said second olefin is ethylene;

27. one of said first polymerization catalysts and said secondpolymerization catalyst produces an oligomer of the formula R⁶⁰ CH═CH₂from said ethylene, wherein R⁶⁰ is n-alkyl; and

28. a branched polyolefin is a product of said polymerization process.

29. This invention also concerns a polymerization catalyst component,comprising:

30. (a) a first active polymerization catalyst for said olefins which isa Fe or Co complex of a ligand of the formula:

31. wherein:

32. R¹, R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or an inert functional group;

33. R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inertfunctional group or substituted hydrocarbyl; and

34. R⁶ and R⁷ are aryl or substituted aryl;

35. (b) a second active polymerization catalyst for said olefins whichcontains one or more transition metals;

36. (c) a catalyst support; and

37. (d) optionally one or more polymerization catalyst activators forone or both of (a) and (b).

38. Also described herein is a polyolefin containing at least 2 ethylbranches, at least 2 hexyl or longer branches and at least one butylbranch per 1000 methylene groups, and provided that said polyolefin hasfewer than 5 methyl branches per 1000 methylene groups.

39. This invention also includes a polyolefin, containing about 20 toabout 150 branches of the formula —(CH₂CH₂)_(n)H wherein n is an integerof 1 to 100, provided that said polyolefin has less than about 20 methylbranches per 1000 methylene groups.

DETAILS OF THE INVENTION

40. In the polymerization processes and catalyst compositions describedherein certain groups may be present. By hydrocarbyl is meant aunivalent radical containing only carbon and hydrogen. By substitutedhydrocarbyl herein is meant a hydrocarbyl group which contains one ormore (types of) substitutents that does not interfere with the operationof the polymerization catalyst system. Suitable substituents in somepolymerizations may include some or all of halo, ester, keto (oxo),amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite,thioether, amide, nitrile, and ether. Preferred substituents are halo,ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine,phosphinite, thioether, and amide. Which substitutents are useful inwhich polymerizations may in some cases be determined by reference toU.S. patent applications Ser. No. 08/991372, filed Dec. 16, 1997 (nowU.S. Pat. No. 5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S.Pat. No. 6,150,482) (and their corresponding World Patent Applications),both of which are hereby included by reference. By an aryl moiety ismeant a univalent group whose free valence is to a carbon atom of anaromatic ring. The aryl moiety may contain one or more aromatic ring andmay be substituted by inert groups. By phenyl is meant the C₆H₅—radical, and a phenyl moiety or substituted phenyl is a radical in whichone or more of the hydrogen atoms is replaced by a substituent group(which may include hydrocarbyl). Preferred substituents for substitutedphenyl include those listed above for substituted hydrocarbyl, plushydrocarbyl. If not otherwise stated, hydrocarbyl, substitutedhydrocarbyl and all other groups containing carbon atoms, such as alkyl,preferably contain 1 to 20 carbon atoms.

41. By a polymerization catalyst activator is meant a compound thatreacts with a transition metal compound to form an active polymerizationcatalyst. A preferred polymerization catalyst activator is analkylaluminum compound, that is a compound which has one or more alkylgroups bound to an aluminum atom.

42. By a polymerization catalyst component is meant a composition thatby itself, or after reaction with one or more other compounds(optionally in the presence of the olefins to be polymerized), catalyzesthe polymerization of olefins.

43. Noncoordinating ions are mentioned and useful herein. Such anionsare well known to the artisan, see for instance W. Beck., et al., Chem.Rev., vol. 88, p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol.93, p. 927-942 (1993), both of which are hereby included by reference.Relative coordinating abilities of such noncoordinating anions aredescribed in these references, Beck at p. 1411, and Strauss at p. 932,Table III. Useful noncoordinating anions include SbF₆ ⁻, BAF, PF₆ ⁻, orBF₄ ⁻, wherein BAF is tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

44. A neutral Lewis acid or a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion is also present as part of thecatalyst system. By a “neutral Lewis acid” is meant a compound which isa Lewis acid capable of abstracting X from (II) to form a weaklycoordination anion.

45. In (II), M is Co or Fe, each X is independently and anion and each Xis such that the total negative charges on X equal the oxidation stateof M. The neutral Lewis acid is originally uncharged (i.e., not ionic).Suitable neutral Lewis acids include SbF₅, Ar₃B (wherein Ar is aryl),and BF₃. By a cationic Lewis acid is meant a cation with a positivecharge such as Ag⁺, H⁺, and Na⁺.

46. In those instances in which (II) does not contain an alkyl orhydride group already bonded to the metal (i.e., X is not alkyl orhydride), the neutral Lewis acid or a cationic Lewis or Bronsted acidalso alkylates or adds a hydride to the metal, i.e., causes an alkylgroup or hydride to become bonded to the metal atom, or a separatecompound is added to add the alkyl or hydride group.

47. A preferred neutral Lewis acid, which can alkylate the metal, is aselected alkyl aluminum compound, such as R⁹ ₃Al, R⁹ ₂AlCl, R⁹AlCl₂, and“R⁹AlO” (alkylaluminoxanes), wherein R⁹ is alkyl containing 1 to 25carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminumcompounds include methylaluminoxane (which is an oligomer with thegeneral formula [MeAlO]_(n)), (C₂H₅)₂AlCl, C₂H₅AlCl₂, and[(CH₃)₂CHCH₂]₃Al. Metal hydrides such as NaBH₄ may be used to bondhydride groups to the metal M.

48. For (I) and (II) preferred formulas and compounds are found in U.S.Patent Applications 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No.5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No.6,150,482), and preferred groupings and compounds in these applicationsare also preferred herein. However the compound numbers and group (i.e.,R^(x)) numbers in these applications may vary from those herein, butthey are readily convertible. These applications also describe synthesisof (I) and (II).

49. There are many different ways of preparing active polymerizationcatalysts from (I) or (II) many of which are described in U.S. patentapplications Ser. Nos. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No.5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No.6,150,482), and those so described are applicable herein. “Pure”compounds which themselves may be active polymerization catalysts may beused, or the active polymerization catalyst may be prepared in situ by avariety of methods.

50. For instance, olefins may be polymerized by contacting, at atemperature of about −100° C. to about +200°C. a first compound W, whichis a neutral Lewis acid capable of abstracting X⁻to form WX⁻, providedthat the anion formed is a weakly coordinating anion; or a cationicLewis or Bronsted acid whose counterion is a weakly coordinating anion.

51. Which first active polymerization catalysts will polymerize whicholefins, and under what conditions, will also be found in U.S. patentapplications Ser. Nos. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No.5,955,555), and 09/006031, filed Jan. 12, 1998 (now U.S. Pat. No.6,150,482). Monomers useful herein for the first active polymerizationcatalyst include ethylene and propylene. A preferred monomer for thiscatalyst is ethylene.

52. In one preferred process described herein the first and secondolefins are identical, and preferred olefins in such a process are thesame as described immediately above. The first and/or second olefins mayalso be a single olefin or a mixture of olefins to make a copolymer.Again it is preferred that they be identical, particularly in a processin which polymerization by the first and second polymerization catalystsmake polymer simultaneously.

53. In some processes herein the first active polymerization catalystmay polymerize a monomer that may not be polymerized by said secondactive polymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molarproportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

54. In another variation of the process described herein one of thepolymerization catalysts makes an oligomer of an olefin, preferablyethylene, which oligomer has the formula R⁶⁰CH═CH₂, wherein R⁶⁰ isn-alkyl, preferably with an even number of carbon atoms. The otherpolymerization catalyst in the process (co)polymerizes this olefin,either by itself or preferably with at least one other olefin,preferably ethylene, to form a branched polyolefin. Preparation of theoligomer (which is sometimes called an α-olefin) by a first activepolymerization-type of catalyst can be found in U.S. patent application09/005965, filed Jan. 12, 1998 (now U.S. Pat. No. 6,103,946)(“equivalent” of World Patent Application 99/02472), and B. L. Small,et. al., J. Am. Chem. Soc., vol. 120, p. 7143-7144 (1998), all of whichare hereby included by reference. These references describe the use of alimited class of compounds such as (II) to prepare compounds of theformula R⁶⁰CH═CH₂ from ethylene, and so would qualify as a catalyst thatproduces this olefin. In a preferred version of this process one ofthese first-type polymerization is used to form the α-olefin, and thesecond active polymerization catalyst is a catalyst which is capable ofcopolymerizing ethylene and olefins of the formula R⁶⁰CH═CH₂, such as aZiegler-Natta-type or metallocene-type catalyst. Other types of suchcatalysts include transition metal complexes of amidimidates and certainiron or cobalt complexes of (I). The amount of branching due toincorporation of the olefin R⁶⁰CH═CH₂ in the polymer can be controlledby the ratio of α-olefin forming polymerization catalyst to higherpolymer forming olefin polymerization catalyst. The higher theproportion of α-olefin forming polymerization catalyst the higher theamount of branching. The homopolyethylenes that are made may range frompolymers with little branching to polymers which contain many branches,that is from highly crystalline to amorphous homopolyethylenes. In onepreferred form, especially when a crystalline polyethylene is beingmade, the process is carried out in the gas phase. It is believed thatin many cases in gas phase polymerization when both catalysts arepresent in the same particle on which polymerization is taking place(for example originally a supported catalyst), the α-olefin isespecially efficiently used (polymerized into the resulting polymer).When amorphous or only slightly crystalline homopolyethylenes are beingmade the process may be carried out in liquid slurry or solution.

55. In the variation of the process described in the immediatelypreceding paragraph a novel homopolyethylene is produced. By“homopolyethylene” in this instance is meant a polymer produced in apolymerization in which ethylene is the only polymerizable olefin addedto the polymerization process in a single step, reactor, or bysimultaneous reactions. However it is understood that the polymerproduced is not made by the direct polymerization of ethylene alone, butby the copolymerization of ethylene and α-olefins which are produced insitu. The polymer produced usually contains only branches of the formula(excluding end groups) —(CH₂CH₂)_(n)H wherein n is 1 or more, preferably1 to 100, more preferably 1 to 30, of these branches per 1000 methyleneatoms. Normally there will be branches with a range of “n” in thepolymer. The amount of these branches (as measured by total methylgroups) in the polymer preferably ranges from about 2 to about 200,especially preferably about 5 to about 175, more preferably about 10 toabout 150, and especially preferably about 20 to about 150 branches per1000 methylene groups in the polymer (for the method of measurement andcalculation, see World Patent Application 96/23010). Another preferablerange for these branches is about 50 to about 200 methyl groups per 1000methylene carbon atoms. It is also preferable (either alone or incombination with the other preferable features above) that in thesebranched polymers there is at least 2 branches each of ethyl and n-hexylor longer and at least one n-butyl per 1000 methylene groups, morepreferably at least 4 branches each of ethyl and n-hexyl or longer andat least 2 n-butyl branches per 1000 methylene groups, and especiallypreferably at least 10 branches each of ethyl and n-hexyl or longer andat least 5 n-butyl branches per 1000 methylene groups. It is alsopreferred that there are more ethyl branches than butyl branches in thishomopolyethylene. In another preferred polymer (alone or in combinationwith any of the above preferred features) there is less than 20 methylbranches, more preferably less than 2 methyl branch, and especiallypreferably less than 2 methyl branches (all after correction for endgroups) per 1000 methylene groups.

56. In the polymerizations to make the “homopolyethylene” only a singlehigh molecular weight polymer is produced, that is a polymer which hasan average degree of polymerization of at least 50, more preferably atleast 200, and especially preferably at least 400. The synthesis of thebranched homopolyethylene is believed to be successful in part becausethe catalyst which produces the α-olefin often does so at a ratecomparable with the polymerization rate, both of them, for the sake oflow cost, being relatively rapid.

57. Likewise, conditions for such polymerizations, particularly forcatalysts of the first active polymerization type, will also be found inall of these patent applications. Briefly, the temperature at which thepolymerization is carried out is about −100° C. to about +200° C.,preferably about −20° C. to about +80° C. The polymerization pressurewhich is used with a gaseous olefin is not critical, atmosphericpressure to about 275 MPa, or more, being a suitable range. With aliquid monomer the monomer may be used neat or diluted with anotherliquid (solvent) for the monomer. The ratio of W:(I), when W is present,is preferably about 1 or more, more preferably about 10 or more whenonly W (no other Lewis acid catalyst) is present. These polymerizationsmay be batch, semi-batch or continuous processes, and may be carried outin liquid medium or the gas phase (assuming the monomers have therequisite volatility). These details will also be found in U.S. patentapplications Ser. No. 08/991372, filed Dec. 16, 1997 (now U.S. Pat. No.5,955,555), and 09/006031, filed Jan. 12, 1998, and 09/005965, filedJan. 12, 1998 (now U.S. Pat. No. 6,150,482).

58. In these polymerization processes preferred groups for R⁶ is

59. and for R⁷ is

60. wherein:

61. R⁸ and R¹³ are each independently hydrocarbyl, substitutedhydrocarbyl or an inert functional group;

62. R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or an inert functional group;

63. R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or an inert functional group;

64. and provided that any two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵,R¹⁶ and R¹⁷ that are vicinal to one another, taken together may form aring.

65. Two chemically different active polymerization catalysts are used inthe polymerization described herein. The first active polymerizationcatalyst is described in detail above. The second active polymerizationcatalyst may also meet the limitations of the first activepolymerization catalyst, but must be chemically distinct. For instance,it may have a different transition metal present, and/or utilize aligand which differs in structure between the first and second activepolymerization catalysts. In one preferred process, the ligand type andthe metal are the same, but the ligands differ in their substituents.

66. Included within the definition of two active polymerizationcatalysts are systems in which a single polymerization catalyst is addedtogether with another ligand, preferably the same type of ligand, whichcan displace the original ligand coordinated to the metal of theoriginal active polymerization catalyst, to produce in situ twodifferent polymerization catalysts.

67. However other types of catalysts may also be used for the secondactive polymerization catalyst. For instance so-called Ziegler-Nattaand/or metallocene-type catalysts may also be used. These types ofcatalysts are well known in the polyolefin field, see for instanceAngew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), EuropeanPatent Application 416,815 and U.S. Pat. No. 5,198,401 for informationabout metallocene-type catalysts, and J. Boor Jr., Ziegler-NattaCatalysts and Polymerizations, Academic Press, New York, 1979 forinformation about Ziegler-Natta-type catalysts, all of which are herebyincluded by reference. Suitable late metal transition catalysts will befound in World Patent Applications 96/23010 and 97/02298, both of whichare hereby included by reference. Many of the useful polymerizationconditions for these types of catalyst and the first activepolymerization catalysts coincide, so conditions for the polymerizationswith first and second active polymerization catalysts are easilyaccessible. Oftentimes the “co-catalyst” or “activator” is needed formetallocene of Ziegler-Natta-type polymerizations, much as W issometimes needed for polymerizations using the first activepolymerization catalysts. In many instances the same compound, such asan alkylaluminum compound, may be used for these purposes for both typesof polymerization catalysts.

68. Suitable catalysts for the second polymerization catalyst alsoinclude metallocene-type catalysts, as described in U.S. Pat. No.5,324,800 and European Patent Application 129,368; particularlyadvantageous are bridged bis-indenyl metallocenes, for instance asdescribed in U.S. Pat. No. 5,145,819 and European Patent Application485,823. Another class of suitable catalysts comprises the well-knownconstrained geometry catalysts, as described in European PatentApplications 416,815, 420,436, 671,404, and 643,066 and World PatentApplication 91/04257. Also the class of transition metal complexesdescribed in WO 96/13529 can be used. Also useful are transition metalcomplexes of bis(carboximidamidatonates), as described in U.S. patentapplication Ser. No. 08/096668, filed Sep. 1, 1998.

69. All the catalysts herein may be “heterogenized” (to form apolymerization catalyst component, for instance) by coating or otherwiseattaching them to solid supports, such as silica or alumina. Where anactive catalyst species is formed by reaction with a compound such as analkylaluminum compound, a support on which the alkylaluminum compound isfirst coated or otherwise attached is contacted with the transitionmetal compounds (or their precursors) to form a catalyst system in whichthe active polymerization catalysts are “attached” to the solid support.These supported catalysts may be used in polymerizations in organicliquids. They may also be used in so-called gas phase polymerizations inwhich the olefin(s) being polymerized are added to the polymerization asgases and no liquid supporting phase is present. The transition metalcompounds may also be coated onto a support such as a polyolefin(polyethylene, polypropylene, etc.) support, optionally along with otherneeded catalyst components such as one or more alkylaluminum compounds.

70. The molar ratio of the first active polymerization catalyst to thesecond active polymerization catalyst used will depend on the ratio ofpolymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

71. The polymers made by the first active polymerization catalyst andthe second active polymerization catalyst may be made in sequence, i.e.,a polymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence.

72. The polymers produced by this process may vary in molecular weightand/or molecular weight distribution and/or melting point and/or levelof crystallinity, and/or glass transition temperature or other factors.For copolymers the polymers may differ in ratios of comonomers if thedifferent polymerization catalysts polymerize the monomers present atdifferent relative rates. The polymers produced are useful as moldingand extrusion resins and in films as for packaging. They may haveadvantages such as improved melt processing, toughness and improved lowtemperature properties.

73. In the Examples, all pressures are gauge pressures.

74. In the Examples the transition metal catalysts were either bought,or if a vendor is not listed, were made. Synthesis of nickel containingcatalysts will be found in World Patent Application 96/23010, whilesynthesis of cobalt and iron containing catalysts will be found in U.S.patent applications Ser. Nos. 08/991372, filed Dec. 16, 1997 (now U.S.Pat. No. 5,955,555) and 09/006031, filed Jan. 12, 1998 (now U.S. Pat.No. 6,150,482).

75. In the Examples PMAO-IP is a form of methylaluminoxane which staysin solution in toluene, and is commercially available. W440 is aZiegler-Natta type catalyst of unknown structure available from AkzoChemicals, Inc., 1 Livingston Ave., Dobbs Ferry, N.Y. 10522, U.S.A.

Examples 1-9 and Comparative Examples A-E Ethylene PolymerizationGeneral Procedure

76. The catalyst was weighed into a reaction vessel and was dissolved inabout 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then ethylene. The PMAO-IP (methylaluminoxane solution) wasthen quickly added to the vessel and the reaction was put under 35 kPaethylene. The reaction ran at room temperature in a water bath to helpdissipate heat from any exotherm. The ethylene was then turned off andthe reaction was quenched with about 15 mL of methanol/HCl solution(90/10 volume %) If polymer was present, the reaction was filtered andthe polymer was rinsed with methanol, then acetone and dried overnightin the hood. The resulting polymer was collected and weighed.

77. Below for each polymerization the catalysts used are listed

Example 1

78. catalyst 1: 4 mg (0.006 mmol)

79. catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

80. co-catalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0 M in toluene

81. duration: 4 h

82. polymer: 5.322 g yield

Example 2

83. catalyst 1: 4 mg (0.006 mmol)

84. catalyst 2: 4 mg (0.006 mmol)

85. cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

86. duration: 4 h

87. polymer: 2.282 g yield

Example 3

88. catalyst 1: 3.5 mg (0.006 mmol)

89. catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog493-4002, 2 mg (0.006 mmol)

90. cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

91. duration: 4 h

92. polymer: 3.651 g yield

Example 4

93. catalyst 1: 3.5 mg (0.006 mmole)

94. catalyst 2: 4 mg (0.006 mmol)

95. cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

96. duration: 4 h

97. polymer: 2.890 g yield

Example 5

98. catalyst 1: 3.5 mg (0.006 mmol)

99. catalyst 2: 4 mg (0.006 mmol)

100. cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0 M in toluene

101. duration: 4 h

102. polymer: 3.926 g yield

Example 6

103. catalyst 1: 4 mg (0.006 mmol)

104. catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmoleof Ti, based on wt %)

105. cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0 M in toluene

106. duration: 4 h

107. polymer: 2.643 g yield

Example 7

108. catalyst 1: 3.5 mg (0.006 mmol)

109. catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmoleof Ti, based on wt %)

110. cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

111. duration: 4 h

112. polymer: 2.943 g yield

Example 8

113. catalyst 1: 4 mg (0.006 mmol)

114. catalyst 2: 4 mg (0.006 mmol)

115. catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

116. cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0 M in toluene

117. duration: 4 h

118. polymer: 6.178 g yield

Example 9

119. catalyst 1: 3.5 mg (0.006 mmol)

120. catalyst 2: 4 mg (0.006 mmol)

121. catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

122. cocatalyst: PMAO-IP; 3.0 mmol Al; 1.5 mL of 2.0 M in toluene

123. duration: 4 h

124. polymer: 4.408 g yield

Comparative Example A

125. catalyst: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

126. cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0 M in toluene

127. duration: 4 h

128. polymer: 2.936 g yield

Comparative Example B

129. catalyst: 4 mg (0.006 mmol)

130. cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0 M in toluene

131. duration: 4 h

132. polymer: 1.053 g yield

Comparative Example C

133. catalyst: 4 mg (0.006 mmol)

134. cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0 M in toluene

135. duration: 4 h

136. polymer: 2.614 g yield

Comparative Example D

137. catalyst: 3.5 mg (0.006 mmol)

138. cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0 M in toluene

139. duration: 4 h

140. polymer: 2.231 g yield

Comparative Example E

141. catalyst: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmole ofTi, based on wt %)

142. cocatalyst: PMAO-IP; 1.0 mmol Al; 0.5 mL of 2.0 M in toluene

143. duration: 4 h

144. polymer: 0.326 g yield

Examples 10-12

145. Propylene Polymerization General Procedure

146. The catalyst was weighed into a reaction vessel and was dissolvedin about 20 mL of distilled toluene. The reaction was sealed andtransferred from the drybox to the hood. The reaction was purged withnitrogen, then propylene. The MAO was then quickly added to the vesseland the reaction was put under 35 kPa propylene. Reaction ran at 0° C.in an ice bath. The propylene was then turned off and the reaction wasquenched with about 15 mL of methanol/HCl solution (90/10 volume %). Ifpolymer was present, the reaction was filtered and the polymer wasrinsed with methanol, then acetone and dried overnight in the hood. Theresulting polymer was collected and weighed.

Example 10

147. catalyst 1: 3 mg (0.006 mmol)

148. catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog#93-4002, 2 mg (0.006 mmol)

149. cocatalyst: PMAO-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

150. duration: 5 h

151. polymer: 0.471 g yield

Example 11

152. catalyst 1: 3 mg (0.006 mmol)

153. catalyst 2: 4 mg (0.006 mmol)

154. cocatalyst: PMAO-IP; 2.0 mmole Al; 1.0 mL of 2.0 M in toluene

155. duration: 5 h

156. polymer: 1.191 g yield

Example 12

157. catalyst 1: 3 mg (0.006 mmol)

158. catalyst 2: W440, from Akzo Nobel, 2.3 wt % Ti, 12 mg (0.006 mmoleof Ti, based on wt %)

159. cocatalyst: PMAQ-IP; 2.0 mmol Al; 1.0 mL of 2.0 M in toluene

160. duration: 5 h

161. polymer: 0.238 g yield

Examples 13-77 and Comparative Examples F-N

162. In these Examples, compounds A-V and 2 were used as the transitionmetal compounds.

163. For preparation of: compound A see B. L. Small, et al., J. Am.Chem. Soc., vol. 120, p. 7143-7144(1998); compound B see Ewen, et al.,J. Am. Chem. Soc., vol. 110, p. 6255-6256(1988); compound C. seeEuropean Patent Application 416,815; compound D World patent Application98/27124; compound E World patent Application 96/23010; compounds G, H,I and R were purchased from Boulder Scientific company; compounds K, Pand 2 were bought from Strem Chemicals Inc.; compound Q was obtainedfrom Aldrich Chemical Co.; compounds S, T, U and V were made byprocedures described in U.S. patent application Ser. No. 08/096668,filed Sep. 1, 1998; compound F was made by reacting ZrCl₄ and the amidelithium salt (see J. Chem. Soc., Dalton Trans. 1994, 657) in etherovernight, and removing the ether and pentane extraction gave F 69%yield; compound J was prepared by modifying the procedure of Journal ofOrganometallic Chemistry 1993, 459, 117-123; compounds L and M wereprepared by following the preparation in Macromolecules, 1995, 28,5399-5404, and Journal of Organometallic Chemistry 1994, 472, 113-118;compound N was made by the procedure described in U.S. Pat. No.5,096,867; and compound O was prepared by following a literatureprocedure (Ferdinand R. W. P. Wild, et al., Journal of OrganometallicChemistry 1985, 288, 63-67).

Examples 13-17 and Comparative Examples F-G

164. A 600 mL Parr® reactor was heated up under vacuum and then allowedto cool under nitrogen. In a drybox, to a Hoke® cylinder was added 5 mLtoluene and a certain amount of PMAO-IP (13.5 wt % toluene solution) asshown in Table 1. To a 20 mL vial was added the ethylene(co)polymerization catalyst and 2 mL toluene. The solution was thenpipette transferred to a 300 mL RB flask, followed by addition of 150 mL2,2,4-trimethyl pentane. If catalyst A was used, its toluene suspensionwas syringe transferred to the flask. The flask was capped with a rubbersepta. Both the Hoke® cylinder and the flask were brought out of thedrybox. Under nitrogen protection, the transition metal compoundsolution was cannulated to the reactor. The reactor was pressurized withnitrogen and then the nitrogen was released. The reactor was heated to70° C., then, pressurized 2× to 690 kPa ethylene, venting each time andfinally pressurized to 970 kPa with stirring. The MAO solution was addedfrom the Hoke® cylinder at slightly higher pressure. The ethylenepressure of the reactor was then adjusted to the desired pressure (Table1). The reaction mixture was allowed to stir for certain period of time(Table 1). The heating source was removed. Ethylene was vented to about210 kPa. The reactor was back filled with 1.4 MPa nitrogen and was thenvented to 210 kPa. This was repeated once. The reaction mixture was thencooled to RT (room temperature). The reaction mixture was then slowlypoured into 400 mL methanol, followed by addition of 6 mL conc. HCl.Upon stirring at RT for 25 min, polymer was filtered, washed withmethanol six times and dried in vacuo.

Examples 18-76 (except Examples 22 and 23) and Comparative Examples H-N

165. General procedure for making silica supported catalysts: In adrybox, one of transition metal compounds (but not A), and compound A(0.1 wt % in biphenyl) and silica supported MAO (18 wt % in Al,Albermarle) were mixed with 15 mL of toluene in a 20 mL vial. The vialwas shaken for 45 minutes at RT. The solid was filtered, washed with 3×5mL toluene and dried in vacuo for 1 hour. It was then stored in afreezer in the drybox and was used the same day.

166. General procedure for gas phase ethylene polymerization by thesupported catalysts using a Harper Block Reactor: In a drybox, supportedcatalysts (5.0 mg or 2.0 mg each, except Example 20 where 15.0 mg wasused) were weighed in GC vials. They were placed in a Harper BlockReactor. The reactor was brought out of the drybox and was charged with1.21 MPa of ethylene. It was then placed in a 90° C. oil bath for 1 hunder 1.12 MPa of ethylene. The reactor temperature reached 85° C. after23 minutes and 87° C. after 35 min. The temperature stayed at 87° C. forthe rest of the reaction. (Time, temperature and pressure for Examplesin Tables 7-9, as noted.) Ethylene was vented. Polymers were weighed andthen submitted for ¹H NMR analysis(TCE-d₂, 120° C.) withoutpurification. Details of these polymerizations are given in Table 2-9.

167. In Table 10, the branching distribution [in branches per 1,000methylene (CH₂) groups] of the product polymers of selected examples aregiven. They were determined by ¹³C NMR (TCB, 120° C.). Methods formeasuring the branching distribution are found in World patentApplication 96/23010.

168. In all the Tables, where provided, branching levels in thepolymers, Me/1000CH₂ groups, methyl groups per 1000 methylene groups inthe polymer, are measured by the method described in World PatentApplication 96/23010. In the Tables PE is polyethylene, TON is moles ofethylene polymerized/mole of polymerization catalysts (total oftransition metal compounds present)/h, Mn is number average molecularweight, PDI is Mw/Mn where Mw is weight average molecular weight, and Pis ethylene pressure. The PMAO-IP used was 13.5 wt. % in toluene. Theamount of residual α-olefin in the polymer was estimated by ¹H NMR, bymeasurement of the vinylic proton signals of the α-olefin. TABLE 1Catalyst, Ex. amount Catalyst A P_(C2H4) Time MMAO PE yield #Me Per m.p.Density(IR) No. (×10⁻⁶ mole) (×10⁻⁶ mole) MPa T(° C.) (min.) (mL) (g)1000 CH₂ (° C.) Mn/PDI (g/cm³) F B, 8.1 0 1.21  70-100 35 4.2 15.0 1 13443,700/2.2 0.952 13 B, 8.1 0.26 1.31 81-96 25 4.2 24.0 17  116, 10332,400/2.2 0.914 G C, 2.2 0 1.1 90 30 1.2 11.0 4 132  11,700/19.7 0.94014 C, 9.5 0.06 1.31 109-126 30 4.8 31.2 8 133 125,000/2.7  0.937 15 C,9.5 0.13 1.34  80-120 36 4.8 30.0 11 119 68,400/2.5 0.922 16 C, 4.6 0.261.3 71-96 25 2.4 10.3 45 121, 56 94,000/2.3 0.895 261/2.8* 17 C, 3.0 2.31.41 100-116 43 1.5 16.6 52 117, 98 65,000/2.1 0.922  84 214/3.4*

169. TABLE 2 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yieldTm No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) #Me/1000 CH₂ (°C.) Mn/PDI TON H B, 0.033 0 1000:1:0   0.195 5 127 24,039/5.2 210,000 IC, 0.033 0 1000:1:0   0.075 4 126 125,451/2.1  82,000 18 B, 0.033 0.0011000:1:0.03 0.485 15 120 48,213/4.1 500,000 19 B, 0.033 0.00331000:1:0.1  0.159 62 125  1,916/24.0 150,000 20 C, 0.099 0.00301000:1:0.03 0.200 35 113 63,534/2.7 70,000 21 D, 0.033 0.00171000:1:0.05 0.228 4 133  2,150/26.2 240,000

170. TABLE 3 Catalyst and Al:M:Fe amount Catalyst A ratio PE Ex. (×10⁻⁶(×10⁻⁶ M = Zr, yield #Me/1000 No. mole) mole) Ti or Fe (g) CH₂ TON J H,0.033 0 1000:1:0 0.421 2 460,000 K I, 0.033 0 1000:1:0 0.135 4 150,000 LG, 0.033 0 1000:1:0 0.420 2 460,000 M K, 0.033 0 1000:1:0 0.091 3 99,000N R, 0.033 0 1000:1:0 0.203 2 220,000

171. TABLE 4 Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Feratio yield #Me/ Tm left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti orFe (g) 1000 CH₂ (° C.) Mn/PDI TON polymer 24 F, 0.033 0.0017 1000:1:0.050.073 66 120   213/18.5 76,000 significant 25 G, 0.033 0.00171000:1:0.05 0.503 13 122, 115 41,525/4.7 520,000 almost none 26 H, 0.0330.0017 1000:1:0.05 0.752 9 120, 115 54,825/4.7 780,000 almost none 27 I,0.033 0,0017 1000:1:0.05 0.562 31 119 72,982/3.2 580,000 almost none 28J, 0.033 0.0017 1000:1:0.05 0.032 54 —   895/5.6 33,000 small amount 29K, 0.033 0.0017 1000:1:0.05 0.240 16 123  1,124/16.5 250,000 smallamount 30 L, 0.033 0.0017 1000:1:0.05 0.112 75 116, 102 — 116,000significant 31 M, 0.033 0.0017 1000:1:0.05 0.092 61 119 — 96,000significant 32 N, 0.033 0.0017 1000:1:0.05 0.068 75 124   485/18.371:000 small amount 33 O, 0.033 0.0017 1000:1:0.05 0.024 15 — — 25,000almost none 34 P, 0.033 0.0017 1000:1:0.05 0.019 12 — — 20,000 smallamount 35 Q, 0.033 0.0017 1000:1:0.05 0.082 40 — — 85,000 significant 362, 0.033 0.0017 1000:1:0.05 0.157 7 — — 160,000 — 37 R, 0.033 0.00171000:1:0.05 0.416 10 122 37,993/7.3 450,000 almost none 38 S, 0.0330.0017 1000:1:0.05 0.056 59 — — 58,000 significant 39 T, 0.033 0.00171000:1:0.05 0.023 73 — — 24,000 significant 40 U, 0.033 0.00171000:1:0.05 0.102 69 — — 110,000 significant 41 V, 0.033 0.00171000:1:0.05 0.059 78 — — 61,000 significant

172. TABLE 5* Catalyst and PE α-olefins Ex. amount Catalyst A Al:M:Feratio yield #Me/ left in No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe(g) 1000 CH₂ Mn/PDI TON polymer 42 D, 0.033 0.0033 1000:1:0.10 0.481 83,346/48.6   360,000 significant 43 D, 0.033 0.0082 1000:1:0.25 0.534 14402/156.0 350,000 significant 44 D, 0.033 0.016 1000:1:0.50 0.566 20800/103.0 310,000 significant

173. TABLE 6 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield#Me/ Tm Density No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000CH₂ (° C.) Mn/PDI TON (g/cm³) 45 H, 0.033 0.0017 1000:1:0.05 0.772 6 12443,791/6.0 800,000 0.930 46 H, 0.013 0.0007 1000:1:0.05 0.367 8 12482,151/3.7 950,000 — 47 I, 0.033 0.0017 1000:1:0.05 0.566 38 11470,462/4.0 590,000 0.909 48 I, 0.013 0.0007 1000:1:0.05 0.226 32 — —590,000 — 49 B, 0.033 0.0010 1000:1:0.03 0.442 8 127 52,673/4.9 460,0000.928 50 B, 0.033 0.0010 1000:1:0.03 0.563 17 120 52,350/4.9 600,000 —51 B, 0.013 0.0004 1000:1:0.03 0.134 16 — — 350,000 — 52 H, 0.033 0.00101000:1:0.03 0.699 — — — 740,000 — 53 N, 0.013 0.0004 1000:1:0.03 0.362 6124 55,102/5.0 960,000 — 54 I, 0.033 0.0010 1000:1:0.03 0.376 15 11898,599/4.0 400,000 — 55 G, 0.033 0.0010 1000:1:0.03 0.665 5 12438,693/6.0 700,000 —

174. TABLE 7 Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield#Me/ Tm No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000 CH₂ (°C.) Mn/PDI TON 56 B, 0.033 0.0017 1000:1:0.05 0.740 22 118, 10154,573/4.0 380,000 57 B, 0.013 0.0007 1000:1:0.05 0.206 24 — — 270,00058 H, 0.033 0.0017 1000:1:0.05 1.158 7 121 92,063/4.9 600,000 59 H,0.013 0.0007 1000:1:0.05 0.651 12 — — 850,000 60 I, 0.033 0.00171000:1:0.05 0.439 24 102 102,798/3.8  230,000 61 I, 0.013 0.00071000:1:0.05 0.390 25 — — 510,000 62 G, 0.033 0.0017 1000:1:0.05 0.871 9121 45,311/4.7 450,000

175. TABLE 8* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yieldNo. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) TON 63 B, 0.0130.0007 1000:1:0.05 0.143 370,000 64 B, 0.013 0.0007 1000:1:0.05 0.115300,000 65 H, 0.013 0.0007 1000:1:0.05 0.305 790,000 66 H, 0.013 0.00071000:1:0.05 0.215 560,000 67 I, 0.013 0.0007 1000:1:0.05 0.093 240,00068 I, 0.013 0.0007 1000:1:0.05 0.108 280,000 69 G, 0.013 0.00071000:1:0.05 0.349 900,000

176. TABLE 9* Catalyst and PE Ex. amount Catalyst A Al:M:Fe ratio yield#Me/ No. (×10⁻⁶ mole) (×10⁻⁶ mole) M = Zr, Ti or Fe (g) 1000 CH₂ Mn/PDITON 70 B, 0.033 0.0017 1000:1:0.05 0.534 37 42,448/3.4 280,000 71 B,0.033 0.0017 1000:1:0.05 0.489 45 — 250,000 72 H, 0.033 0.00171000:1:0.05 0.969 17 77,142/4.8 500,000 73 H, 0.033 0.0017 1000:1:0.051.027 11 — 530,000 74 I, 0.033 0.0017 1000:1:0.05 0.442 34 96,383/4.2230,000 75 I, 0.033 0.0017 1000:1:0.05 0.466 32 — 240,000 76 G, 0.0330.0017 1000:1:0.05 0.710 8 39,693/4 9 370,000

177. TABLE 10 Ex. No. Total Me Me Et Pr Bu Am Hex and higher 15 10.5 04.6 0 2.4 0 4.3 13 16 0 6.5 0 3.2 0 6.5 26 6.9 0 2.9 0 0.4 0 2.5 47 23 08.6 0 4.7 0 10.7 49 8.1 0 3.6 0 1.3 0 3.1

Example 22

178. In a drybox, 1.7 mg Compound E and 1.0 mg Compound A were mixedwith 40 mL toluene in a Schlenk flask. This was brought out of thedrybox and was purged with ethylene for 15 min at 0° C. MAO toluenesolution (0.64 mL 13.5 wt %) was injected. The mixture was allowed tostir under 0 kPa ethylene at 0° C. for 12 min. Methanol (100 mL) wasinjected, followed by 1 mL conc. HCl. Upon stirring for 25 min at RT,the white solid was filtered, washed with 6×20 mL methanol and dried invacuo. White solid (2.9 g) was obtained. ¹HNMR in TCE-d₂ at 120°C.: 44Me/1000 CH₂. The polymer contained a significant amount of α-olefins.

Example 23

179. In a drybox, 30.5 mg of Compound A was mixed with 30.5 g biphenylin a 100 mL Pyrex® glass bottle. This was stirred in a 100° C. bath for25 minutes, during which time Compound A dissolved in biphenyl to form adeep green solution. The solution was allowed to cool down to becomesolid. A 0.1 wt % Compound A/biphenyl homogeneous mixture was obtained.

Example 77

180. A 600 mL Parr® reactor was heated up under vacuum and then allowedto cool under nitrogen. In a drybox, to a 300 mL RB flask was added 150mL 2,2,4-trimethylpentane. The flask was capped with a rubber septum.The flask was brought out of the drybox. Under nitrogen protection, the2,2,4-trimethylpentane solvent was cannulated into the reactor. Thereactor was pressured up with nitrogen and then nitrogen was released.This was repeated one more time. The reactor was heated to 70° C. Thenin a drybox, 160 mg supported catalyst(made by following the generalprocedure of preparing silica supported catalysts, it contained 0.0011mmole of compound B, 0.000057 mmole compound A and 1.1 mmole of MAO) wasmixed with 4 mL cyclohexane and was transferred to a 5 mL gas tightsyringe with long needle. This was brought out of the drybox and wasinjected into the reactor under nitrogen protection (positive nitrogenpressure). The reactor was pressured up with 1.2 MPa of nitrogen, thenreleased to 14 kPa. This was repeated one more time. Under stirring, thereactor was pressured up with ethylene to 1.2 MPa. The reaction mixturewas allowed to stir at between 70° C. to 97° C. for 60 min. Heatingsource was removed. Ethylene was vented to about 210 kPa. The reactorwas back filled with 1.4 MPa nitrogen and was released to 140 kPa. Thiswas repeated twice. The solution was poured into 300 mL methanol. Thepolymer was filtered, washed with 6×50 mL methanol and dried in vacuo.White polymer (19.7 g) was obtained. ¹HNMR in TCE-d₂ at 120° C.:34Me/1000CH₂. Mw=98,991; Mn=35,416(PDI=2.8). Density: 0.902 g/cm³. MeltIndex: 1.03 (190° C.). ^(—)CNMR(120° C., TCE-d₂): Total Me was 29.4(Me=0; Et= 10.8; Pr=0.0; Bu=6.0; Hex and higher=11.7).

What is claimed is:
 1. A compound of the formula

wherein: R¹, R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or an inert functional group; R⁴ and R⁵ areeach independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R⁸,R¹², R¹³ and R¹⁷ are each independently hydrocarbyl, substitutedhydrocarbyl or an inert functional group; R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl oran inert functional group; and provided that any two of R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ that are vicinal to one anothertaken together may form a ring.
 2. The compound as recited in claim 1wherein: R¹, R² and R³ are hydrogen; R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ areeach independently halogen, alkyl containing 1 to 6 carbon atoms, orhydrogen; R⁸, R¹², R¹³ and R¹⁷ is each independently halogen, phenyl oralkyl containing 1 to 6 carbon atoms; and R⁴ and R⁵ are eachindependently hydrogen or alkyl containing 1 to 6 carbon atoms.
 3. Thecompound as recited in claim 2 wherein R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵ and R¹⁶are each hydrogen.
 4. The compound as recited in claim 2 wherein R⁸,R¹², R¹³, and R¹⁷ are each alkyl containing 1-6 carbon atoms.
 5. Thecompound as recited in claim 3 wherein R⁸, R¹², R¹³, and R¹⁷ are eachalkyl containing 1-6 carbon atoms.
 6. The compound as recited in claim 2wherein R⁴ and R⁵ are each hydrogen or methyl.
 7. The compound asrecited in claim 2 wherein R¹, R², R³, R⁹, R¹¹, R¹⁴ and R¹⁶ arehydrogen, R⁴, R⁵, R⁸, R¹⁰, R¹², R¹³, R¹⁵ and R¹⁷ are methyl.
 8. Thecompound as recited in claim 2 wherein R¹, R², R³, R⁹, R¹⁰, R¹¹, R¹⁴,R¹⁵ and R¹⁶ are hydrogen, R⁴ and R⁵ are methylthio, and R⁸, R¹², R¹³ andR¹⁷ are i-propyl.
 9. The compound as recited in claim 2 wherein R¹, R²,R³, R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are hydrogen, R⁴ and R⁵ are1-imidazolyl, and R⁸, R¹², R¹³ and R¹⁷ are i-propyl.
 10. The compound asrecited in claim 2 wherein R¹, R², R³, R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶are hydrogen, R⁸ and R¹³ are chloro, and R⁴, R⁵, R¹² and R¹⁷ are methyl.11. The compound as recited in claim 2 wherein R¹, R², R³, R⁹, R¹⁰, R¹¹,R¹⁴, R¹⁵ and R¹⁶ are hydrogen, R⁴ and R⁵ are methyl, and R⁸, R¹², R¹³and R¹⁷ are i-propyl.
 12. The compound as recited in claim 2 wherein R⁸,R¹², R¹³ and R¹⁷ are each phenyl.
 13. The compound as recited in claim 3wherein R⁸, R¹², R¹³ and R¹⁷ are each phenyl.
 14. The compound asrecited in claim 6 wherein R⁸, R¹², R¹³ and R¹⁷ are each phenyl.
 15. Thecompound as recited in claim 1 wherein R⁸, R¹², R¹³ and R¹⁷ are eachindependently halogen, phenyl or alkyl containing 1 to 6 carbon atoms.16. The compound as recited in claim 15 wherein R⁸, R¹², R¹³ and R¹⁷ areeach phenyl.
 17. The compound as recited in claim 15 wherein: R¹, R² andR³ are hydrogen; and R⁴ and R⁵ are each independently hydrogen or alkylcontaining 1 to 6 carbon atoms.
 18. The compound as recited in claim 16wherein: R¹, R² and R³ are hydrogen; and R⁴ and R⁵ are eachindependently hydrogen or alkyl containing 1 to 6 carbon atoms.
 19. Thecompound as recited in claim 1 wherein: R⁹, R¹¹, R¹⁴ and R¹⁶ are eachhydrogen; and R⁸, R¹⁰, R¹², R¹³, R¹⁵ and R¹⁷ is each independently analkyl containing 1 to 6 carbon atoms.
 20. The compound as recited inclaim 19 wherein: R¹, R² and R³ are hydrogen; and R⁴ and R⁵ are eachindependently hydrogen or alkyl containing 1 to 6 carbon atoms.